Cement composition and method of making same



COAT MG 03 PLASTlC Patented Aug. 28, 1945 Examine:

CEMENT COMPOSITION AND METHOD OF MAKING SAME Edward W. Scripture, J r., Shaker Heights, 01110 No Drawing. Application July 17, 1942, Serial No. 451,323

19 Claims.

This invention relates to a cement composition,

a commsition for grinding cement, and particular y to a method of grinding cement wherein the rate of grinding may be increased with existing equipment.

Hydraulic cements are manufactured by mixing together in a finely divided state, in suitable proportions, either by a wet process or a dry process, suitable raw materials, usually of a calcareous and a silicious nature, to produce after the manufacturing operation chemical compounds having hydraulic and cementitious properties in the desired proportions. The mixed raw materials are heated together in a kiln, in modern practice usually a rotary kiln, and burned at a temperature which causes sintering, or in some cases they may be burned to actual fusion. After burning the 5 a method for grinding cements, wherein the time required to reduce cement clinker to a given surface area is reduced.

It is another object of this invention to provide a method wherein the finer grinding of cement clinker and the production of a cement of greater surface area are facilitated.

It is another object of this invention to provide a ground cement clinker which shall have improved plastic and hydraulic properties.

It is a further object of the present invention resultant product, usually called clinker," is allowed to cool. In this state of manufacture the cementitious compounds have been formed but exist in a physical state, that of relatively large pieces with very low surface area, in which they cannot be used to make mortar or concrete mixes. This cement clinker is then reduced by grinding, usually in a ball mill of either the intermittent or continuous type, to a relatively fine state of subdivision having a relatively large surface area. During this stage, calcium sulfate in one form or another is usually added to the cement to prevent too rapid set.

The hydraulic properties of the cement depend on its chemical composition and on the burning operation, but also to a considerable extent on the grinding and the degree of fineness to which it has been reduced. For example, the plastic properties and the rate at which the cement hydrates are markedly affected by the surface area, i. e., the degree of grinding.

The grinding of cement clinker requires the use of considerable equipment and consumes a substantial period of time. In order to operate the equipment, power in one form or another is required. The grinding operation, therefore, adds substantially to the cost of manufacture of cement and it will be obvious that the finer the grinding the greater will be this cost.

It has heretofore been known that certain materials when added to cement clinker in the mill will facilitate grinding and will increase the emciency of this operation. In rder to be useful, such materials must not have an adverse effect on the plastic or hydraulic properties of the cement, as by retarding or preventing hydration. It is preferable that such materials, which may be termed grinding aids, shall improve the properties of the cement and of the mortar or concrete in which they are used with respect to strength, rate of hardening, plasticity, durability, or other properties.

It is an object of this invention to provide a to provide an indurating composition for cement. It is a still further object of the presentinvention to provide an indurating composition which will improve the properties of concrete, mortar and the like made from hydraulic cement mixes containing pozzolanic materials, acceleratin a ents, dis rsm a en etc. insuita5le amounts.

Some grinding aids heretofore proposed are hygroscopic and when incorporated in the cement in amounts proposed adversely affect the keeping or storing properties of the cement by absorbing moisture from the atmosphere. It is, therefore, another object of the present invention to provide a method for grinding cement wherein the cost of grinding is reducedand whereby the storing or keeping qualities of the cement produced are not impaired. I

In my prior application Serial No. 406,904, filed August 14, 1941, and Patent 2,264,336 issued December 2, 1941, I disclosed that certain aromatic commungs, including the substitutedbe nz oic acids, improve a concrete or cement mix when incorporated therein, and when incorporated with cement clinker reduce the grinding timg and 40 power required to obtain a cement with a given surface area.

It has now been found that the above objects are also accomplished by incorporating in the cement, and preferably by incorporating with the cement clinker in the grinding mill a relatively small percentage, based on the weight of the cement, of a saturated aliphatic compound, consisting of a carBon-to-carB'dn chain of at least fggg agmn atoms and preferab y less than twe V;

carbon atoms. T e saturated aliphatic compound as a ac ed 0 one or more carbon atoms, besides hydrogen, at least one and preferably two hydroxzl groans an preciable deleterious effect on the grinding efll- 60 ciency of the compound. The chain of carbon d at least one prima One or more additional groups NH2) r selec e rom atoms may be straight or branched, as desired, creased. In this manner the time required, and and preferably should not substantially exceed consequently, the power input, to grind to a par- \twelve carbon atoms. ticular degree of fineness or surface area is re- The compounds I have found to be effective duced, or for a given time and power input the dehave the general formula 5 gree of fineness or surface area is increased.

It may be that the reason these compounds having two or more solubilizing groups ofier advantages over compounds having a Single solubilizing OH group is that these two lyophilic groups are adwhere is a member of t e greup consisting f sorbed on the surface of the cement particles. By alkylene groups having four o more carbon the o ption of two group placed at dlfl' r nt atoms and such alkylene groups having one or points in the molecule the molecule itself would more hydrogen t t t by one or more of t be expected to assume a more or less horizontal functional and the non-functional groups or prefposition with relation to the cement oartwles, erably a member of the group consisting of ulrather than a more or less vertical position, as fate, sulfonic acid, sulfonate, halogen, nitro, nimight be expected if only a single group e a $11350I hydroxyl and primary amino groups. SOIbBd. order to prevent folding Of a com- The alkylen'e groups may have straight or Pound havlng four or more f It is T ems of t general formula preferable when only two solubilizmg or polar groups are present that at least one such group be attached to carbon atoms intermediate or bewhere m is at least four and preferably less than tween the terminal carbon atoms. For the same than twelve. Examples of such groups are: reason, it is also desirable that the carbon atoms containing solubilizing or polar groups be separated by one or more carbon atoms. In this manner a given amount of the reagent would cover a CHzCHzCH2CH2 larger surface area of a cement particle, i. e., a *CHPCHPCHPCHPCHP smaller amount would be required to produce a CH -CH-CHz given effect.

(3B3 The preferred number of solubilizing substituenst depends largely on the length of the chain L E Q and upon the number of carbon atoms in the compound, increasing when the number of carbon atoms or the chain length are increased. etc. In the preferred substituted alkylene gro p It would appear very desirable that the amount one Or even more of th hy atoms is subof a grinding aid added to the cement clinker stituted by a member o the group consisting. should be as small as is consistent with efiective sulfate, sulfonic acid, sulfonate, halogen, nitro, r lts, Possibly thi amount is the amount renitroso, hy r yl and primary amino g o p quired to form an adsorbed layer one molecule a y, e b t t ts in the rb -t 40 thick. If a layer of considerable thickness is built bon 0 ydrocarbon chains are sep ted y a up on the cement particles, it would be expected bOn t S having no substituent- Usually i t that this layer would interfere with the subsequent more desirable compounds there is at least one of re ti ns f the cement With any hygroscopic the solubilizing subst t ts Present for e e substance a. relatively thick layer on the cement or six carbon atoms. particles would tend to take up a large amount of The y c p P perties of the compou water, and thus impair the keeping qualities of the depend largely on the number of hydroxyl groups cement, and which would become partially bya d upon the length of the carbon-to-carbon drated during storage. Withavery small amount chain, increasing when the number of hyd oxyl of hygroscopic compound this effect would not be groups increases and decreasing when the numappreciably injurious.

ber of carbon atoms increases. A branched chain Where the compound used as grinding aid is compound appears to be less hygroscopic than a held to the cement particles in a more or less n, v

straight chain com und of the same length; a horiggntal position, rather than in a vertical a. Branched cHain compound also appears more medwtion, the thickness of the layer r )v soluble than a straight chain compound of the quired will be markedly less. It may b sur- 1 same number of carbon atoms, hence branched is d th t, beyond a complete coverage of the 'n. chain mpou ds are u ua y pr r In a y surfaces of the cement particles, further improvemt least four carbon atoms is dement in grinding qualities will be negligible. sirable to reduce the hygroscopic properties of the The following compounds are exam les of Compound, particularly where more than one hy- 6 those included by the above general formula and y group is present. found to be effective in accomplishing the objects It has been observed that in the grinding of ceof the present invention: & ment clinker the balls, in a ball mill, and the walls 2 amino 2 methyl 1'3 propanediol;

of the mill tend to become coated with the more or less finely ground cement. This formation on the grinding surfaces apparently exerts a cush- 2 ammo l butanol, and ig i fgh f gg gfi g rate of grinding 1s Tris (hydroxymethyl) aminomethane.

Although I do not offer this explanation as a The saving in grinding time depends to a large necessary explanation of the results of the present extent both on the quantity of the above described invention, I have found that when small amounts compounds, which are present in the cement, of these chemical compounds are added to cement and on the degree of fineness desired in the clinker in a ball mill, the formation of a cushion cement. With an increase in quantity of the on the grinding surfaces appears to be reduced above described compounds added to the mill and the eliiciency of the grinding operation is in- 7 from effective amounts, such as about .00520,

2 amino 2 ethyl 1,3 propanediol; 2 amino 2 methyl 1 propanol;

we. Cllliutsiiuiib',

COAT? 35 OR PLASTV. Ex

based on the weight of the cement, up to about .05% or .1%, an increase in the efllciency in grinding time may be had. Although as much as .3% to .5% of the above compounds may be incorporated with the cement clinker, appreciable further improvement in results is not obtained and unless the proportion of hydroxyl groups to carbon atoms is less than one-half, the hygroscopicity may be troublesome even though four or more carbon atoms are present in the compounds. It is generally preferable to use less than .05%, such as 045%, of the addition as most of the benefits are obtained with a saving in cost. When the cement is ground to a greater surface area, the saving in the grinding time over processes of the prior art is substantially increased.

The following example illustrates the effect of the compounds of the above general formula in reducing the grinding time or in increasing the s onic aci s, wetting agents, suc

included by the above designated general formula into the cement during the grinding operation. It has been found that when they were thus incorporated, greater improvement in the cement may be obtained. However, a substantial improvement in the cement or concrete mix may be had when the above compounds are added to the ground cement at later stages.

Cement dispersing agents, such as active ingredients of waste s e li uor, naphthalene so i su a e am metal sulfates or s'i'ilfonates, and ccglcrators, suc cmoride and other metal lifo'rides or electrolytes masing the rate of hardening o'r setting lo the cement, pozzolanic materials, etc. may, of course, also be incorporated in the cement mix,

if desired. One or more of the above organic communds may also be mixed with suitable surface area of the cement: 2o amounts of an accelerator, such as calcium chlo- E l ride, and/or cement dispersing and/or wetting ramp elj agents. While calcium chloride or other hygro- Several separate batches of the same amount of identical cement clinker were separately ground for two hours in the same cement mill. One batch served as a control and contained no organic addition. The surface areas of the cements produced and the additions are indicated in the following table:

scopic compounds may be added to the cement at the time of use, it is not usually desirable to add such hygroscopic substances to the clinker before or during grinding, as the keeping qualities of the cement produced would be reduced. A particularly desirable mixture for addition to cement may contain the solid constituents of waste sulphite liquor or ot er cement ispersing agent, and calcium chloride, with the ingredients Batch Addmn Surface proportioned to give in a cement mix .005% to sq cm [W .1% on the weight of the cement of one or more 1 None 1,5 of the compounds included by the above general 2 3% 2 2 methyl formula, 001% to .5% of the solid constituents a .o 0 mim 2 ethyl 3 pro- 1,894 of a cement dispersing agent such as waste sul- E EE; phite liquor residue, and the usual amounts, suc

I prefer to use a proportion of the above compound less than .05% of the weight of the cement, but a proportion up to .1% is not injurious. The beneficial effects of this invention are not secured unless an appreciable amount of the compound, say .005% is used.

The above compounds far from having a deleterious effect improves the properties of concrete structures prepared from cement containing one or more of them in admixtures therewith.

The following example illustrates the improvement of concrete or mortar mixes by the addition of compounds embodying the present invention:

Example as up 0 o, o c c um chloride. If desired, the waste sulphite liquor may be substituted by other cement dispersing agents, or even wetting agents, such as lauryl sodium sulfate. aste sulphite liquor or the dried residue thereof contains watersoluble, active ingredients which function to disperse cement particles in water. While the whole waste sulphite liquor, or the dried residue ER of, which is more conveniently handled, may be .used, the cement dispersing components of the liquor or residue may be substitufid, if desired. In referring to the solid constituents of waste sulphite liquor this expression is used to designate one or more of the active ingredients thereof, either dry or in water.

It will be apparent that a compound which facilitates grinding may be added to the cement clinker in its natural physical form or in solution, or in any other physical form. It will also be apparent that more or less of the usual amountv of gypsum or other form of calcium sulfate may be added, depending on the desired characteristics of the cement, and that other substances may be added to the cement at the same time, or subsequently.

Furthermore it is to be understood that the as particular form of product shown and described compressivestrengm and the particular procedure set forth are pre- Batch Addition sented for purposes of explanation and illustra- 1 day 3 days 7 days 28am, tion, and that various modifications of said product and procedure can be made without depart- Nom 1,340 1,980 2,810 7 ing from my invention as defined in the appended 2.--.-i .045%2amino2meth 1 670 1,980 2,950 3,145 m 3 $15 2,260 3,160 4,030 atlclaim is:

E -EH 1. In the process of grinding cement clinker, the step which comprises grinding the clinker in It is preferred to incorporate the compounds the presence of about .005% to about .1%, based hazrl on the weight of the cement, of 2 amino 2 methyl 1,3 propanediol.

2. A dry cement comprising about .005% to about .l%, based on the weight of the cement, of 2 amino 2 methyl 1,3 propanediol.

3. In the process of grinding cement clinker, the step which comprises grinding the clinker in the presence of about .005% to about .l%, based on the weight of the cement, of 2 amino 2 ethyl 1,3 propanediol.

4. A dry cement comprising about .005% to about .1 based on the weight of the cement, of 2 amino 2 ethyl 1,3 propanediol.

5. In the process of grinding cement clinker, the step which comprises grinding the cement clinker in the presence of a small amount of an aliphatic amino alcohol consisting of carbon-tocarbon chain of at least four and not substantially more than twelve carbon atoms and consisting of carbon, hydroxyl, hydrogen, and one primary amino group.

6. In the process of grinding cement clinker, the step which comprises grinding the clinker in the presence of from about .005% to about .1%

based on the weight of the cement, of an aliphatic compound of the general formula R-NH2, where R is an aliphatic chain of at least four and not substantially more than twelve carbon atoms consisting of carbon, hydrogen and hydroxyl.

7. In the process of grinding cement clinker, the step which comprises grinding the clinker in the presence of from about .005% to about .1%, based on the weight of the cement, of an aliphatic compound of the general formula where R is an aliphatic chain of four to twelve carbon atoms consisting of carbon, hydrogen and one hydroxyl group.

8. In the process of grinding cement clinker, the step which comprises grinding the clinker in the presence of from about .005% to about .1 based on the weight of the cement, of an aliphatic compound of the general formula where R is a saturated aliphatic carbon to carbon chain of at least four and not substantially more than twelve carbon atoms, and consisting of carbon and hydrogen.

'9. In the process of grinding cement clinker, the step which comprises grinding the clinker in the presence of from about .005% to about .1%, based on the weight of the cement, of an aliphatic compound of the general formula about .l% based on the weight of the cement, of an aliphatic compound of the general formula R-NHz, where R is an aliphatic chain consisting of carbon hydroxyl and hydrogen.

12. A dry cement comprising about .005% to about .1% based on the weight of the cement, of an aliphatic compound of the general formula where R is an aliphatic chain consisting of carbon, hydrogen and one hydroxyl group.

13. A concrete or mortar mix comprising sand, aggregate, an hydraulic cement and a small amount of an aliphatic compound, having a carbon-to-carbon chain of at least four and not substantiall more than twelve carbon atoms and consisting of carbon, hydrogen, hydroxyl and one primary amino group.

14. A concrete or mortar mix comprising sand, aggregate, an hydraulic cement and a small amount of an aliphatic compound of the general formula R-NH2, where R is an aliphatic chain consisting of carbon, hydrogen and hydroxyl.

15. A concrete or mortar mix comprising sand, aggregate, an hydraulic cement and a small amount of an aliphatic compound of the general formula where R is an aliphatic chain consisting of carbon, hydrogen and one hydroxyl group.

16. An indurating composition for addition to cement comprising a cement dispersing agent consisting of active ingredients of waste sulphite liquor and an aliphatic amino alcohol, consisting of a carbon-to-carbon chain of at least four and not substantially more than twelve carbon atoms, and consisting of carbon, hydrogen, hydroxyl and one primary amino group, said aliphatic alcohol and said dispersing agent being proportioned to give in a cement mix .005% to .1%, based on the weight of the cement, of said aliphatic alcohol and at the same time .001% to .5% based on the weight of the cement, of said cement dispersing agent.

17. An indurating composition for addition to cement comprising a cement dispersing agent consisting of active ingredients of waste sulphite liquor and an aliphatic compound of the general formula R--NH2, where R is an aliphatic chain consisting of carbon, hydroxyl and hydrogen, said aliphatic compound and said dispersing agent being proportioned to give in a cement mix .005% to .1 based on the weight of the cement, of said aliphatic compound and at the same time .001% to .5%, based on the weight of the cement, of said cement dispersing agent.

18. An indurating composition for addition to cement comprising a cement dispersing agent consisting of active ingredients of waste sulphite liquor and an aliphatic compound of the general formula where R is an aliphatic chain consisting of carbon, hydrogen and one hydroxyl group, said aliphatic compound and said dispersing agent being proportioned to give in a cement mix .005% to 1 to. u

"LZLTZQMS,

CO A TsNG OR PLASTEC inn-""- .1%, based on the weight 0! the cement, of said aliphatic compound and at the same time .001% to 5%, based on the weight of the cement, of said cement dispersing agent.

19. An indurating composition for addition to cement comprising solid active constituents of waste sulphite liquor and an aliphatic primary amino alcohol consisting of a carbon-to-carbon chain at least four and not substantially more than twelve carbon atoms, and consisting of carbon, hydroxyl, hydrogen and one primary amino group, said aliphatic alcohol and said waste sulphite liquor being proportioned to give in a. cement mix .005% to .1% based on the weight of the cement, of said aliphatic alcohol and at the same time .001% to 5%, based on the weight of the cement, of said solid active constituents.

EDWARD W. SCRIPTURE, JR. 

